U.S. patent number 11,286,397 [Application Number 16/606,133] was granted by the patent office on 2022-03-29 for alcohol-based dry-erasable ink.
This patent grant is currently assigned to SOCIETE BIC. The grantee listed for this patent is SOCIETE BIC. Invention is credited to Carine Bethouart, Christelle Debrauwer, Philippe Lefebvre.
United States Patent |
11,286,397 |
Bethouart , et al. |
March 29, 2022 |
Alcohol-based dry-erasable ink
Abstract
An alcohol-based dry-erasable ink for a writing instrument
including, as separation agent, a mixture of glycerol, glycol and
pentaerythritol ester.
Inventors: |
Bethouart; Carine
(Neufchatel-Hardelot, FR), Lefebvre; Philippe
(Wimereux, FR), Debrauwer; Christelle (Saint Germain
sur Morin, FR) |
Applicant: |
Name |
City |
State |
Country |
Type |
SOCIETE BIC |
Clichy |
N/A |
FR |
|
|
Assignee: |
SOCIETE BIC (Clichy,
FR)
|
Family
ID: |
59253709 |
Appl.
No.: |
16/606,133 |
Filed: |
April 16, 2018 |
PCT
Filed: |
April 16, 2018 |
PCT No.: |
PCT/FR2018/050953 |
371(c)(1),(2),(4) Date: |
October 17, 2019 |
PCT
Pub. No.: |
WO2018/193197 |
PCT
Pub. Date: |
October 25, 2018 |
Prior Publication Data
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|
|
|
Document
Identifier |
Publication Date |
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US 20200048484 A1 |
Feb 13, 2020 |
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Foreign Application Priority Data
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|
|
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Apr 18, 2017 [FR] |
|
|
1753341 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B43K
1/12 (20130101); C09D 11/16 (20130101); C09D
11/17 (20130101); B43K 8/022 (20130101) |
Current International
Class: |
B43K
1/12 (20060101); C09D 11/17 (20140101) |
Field of
Search: |
;106/31.01,31.13 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1029144 |
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Apr 1978 |
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CA |
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3044036 |
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May 1982 |
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DE |
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0551913 |
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Jul 1993 |
|
EP |
|
2212408 |
|
Jul 1974 |
|
FR |
|
H0428777 |
|
Jan 1992 |
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JP |
|
H069917 |
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Jan 1994 |
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JP |
|
2010-209169 |
|
Sep 2010 |
|
JP |
|
2010209169 |
|
Sep 2010 |
|
JP |
|
WO 2008/006542 |
|
Jan 2008 |
|
WO |
|
WO 2018/193196 |
|
Oct 2018 |
|
WO |
|
WO 2020/064652 |
|
Apr 2020 |
|
WO |
|
Other References
English translation of JPH 06/9917, Jan. 1994; 7 pages. cited by
examiner .
English translation of JPH 04/28777, Jan. 1992; 5 pages. cited by
examiner .
English translation of JP 2010/209169, Sep. 2010; 7 pages. cited by
examiner .
English translation of DE 3044036, May 1982; 11 pages. cited by
examiner .
International Search Report dated Jun. 15, 2018, in International
Application No. PCT/FR2018/050952 (5 pages). cited by applicant
.
International Search Report dated Jun. 6, 2018, in International
Application No. PCT/FR2018/050953 (5 pages). cited by
applicant.
|
Primary Examiner: Mcdonough; James E
Attorney, Agent or Firm: Bookoff McAndrews, PLLC
Claims
The invention claimed is:
1. An alcohol-based dry-erasable ink for a writing instrument
comprising, as separation agent, a mixture of glycerol, glycol and
a pentaerythritol ester, wherein the pentaerythritol ester is
pentaerythrityl tetraethylhexanoate.
2. The dry-erasable ink according to claim 1, wherein the
pentaerythritol ester content is between 0.1 and 25% by weight in
relation to a total weight of the ink.
3. The dry-erasable ink according to claim 1, wherein the glycol
content is between 0.1% and 5% by weight in relation to a total
weight of the ink.
4. The dry-erasable ink according to claim 1, wherein the glycerol
content is between 0.1% and 10% by weight in relation to a total
weight of the ink.
5. The dry-erasable ink according to claim 1, wherein the alcohol
is an alcohol including R.sub.4--OH in which R.sub.4 represents a
C.sub.1-C.sub.6 alkyl group selected from the group consisting of
ethanol, propanol and mixtures thereof.
6. The dry-erasable ink according to claim 1, wherein the alcohol
content is between 40% and 90% by weight in relation to a total
weight of the ink.
7. The dry-erasable ink according to claim 1, further including a
pigment, a resin and additives.
8. The dry-erasable ink according to claim 7, wherein the additive
is selected from the group consisting of surfactants, manufacturing
additives, denaturing agents, marker tip drying retarders and
mixtures thereof.
9. The dry-erasable ink according to claim 7, wherein the pigment
content is between 0.1% and 10% by weight in relation to a total
weight of the ink.
10. The dry-erasable ink according to claim 7, wherein the resin
content is between 0.1% and 10% by weight in relation to a total
weight of the ink.
11. The dry-erasable ink according to claim 7, wherein the additive
content is between 0.1% and 10% by weight in relation to a total
weight of the ink.
12. A writing instrument including a fibrous tip and comprising a
dry-erasable ink according to claim 1.
13. An alcohol-based dry-erasable ink for a writing instrument
comprising a separation agent, the separation agent consisting
essentially of glycerol, glycol, and a pentaerythritol ester,
wherein the pentaerythritol ester includes pentaerythrityl
tetraethylhexanoate, pentaerythrityl tetracaprylate,
pentaerythrityl tetracaprate, or mixtures thereof.
14. The dry-erasable ink according to claim 13, wherein the glycol
is triethylene glycol.
15. The dry-erasable ink according to claim 13, wherein the
pentaerythritol ester content is between 0.1 and 25% by weight in
relation to a total weight of the ink.
16. The dry-erasable ink according to claim 13, wherein the glycol
content is between 0.1% and 5% by weight in relation to a total
weight of the ink.
17. An alcohol-based dry-erasable ink for a writing instrument
comprising a separation agent, the separation agent comprising a
mixture of glycerol, glycol, and a pentaerythritol ester, wherein
the pentaerythritol ester includes pentaerythrityl
tetraethylhexanoate, pentaerythrityl tetracaprylate,
pentaerythrityl tetracaprate, or mixtures thereof.
18. The dry-erasable ink according to claim 17, wherein the
glycerol content is between 0.1% and 10% by weight in relation to a
total weight of the ink.
19. The dry-erasable ink according to claim 17, wherein the glycol
content is between 0.1% and 5% by weight in relation to a total
weight of the ink.
20. The dry-erasable ink according to claim 17, wherein the
pentaerythritol ester content is between 0.1 and 25% by weight in
relation to a total weight of the ink.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a National Stage application of International
Application No. PCT/FR2018/050953, filed on Apr. 16, 2018, now
published as WO/2018/193197 and which claims priority to French
Application No. 1753341, filed Apr. 18, 2017.
FIELD
The present disclosure relates to an alcohol-based dry-erasable ink
for a writing instrument.
DESCRIPTION OF RELATED ART
Dry-erasable inks are designed to be used on impermeable surfaces
such as whiteboards, e.g. Velleda.RTM.. In most cases, these are
pigmented inks with a low viscosity (between 5 and 10 cP at
20.degree. C.) for use particularly in markers provided with
fibrous tips. They dry quickly and are easily erasable by rubbing
after drying, e.g. using a dry cloth or a brush.
One of the important properties of this type of ink is precisely
their erasure properties over time. The user can erase a whiteboard
even after several days, weeks or even months.
These erasure properties may differ according to the surface
material of whiteboards: polypropylene, PVC, gloss, enamel or
melamine, for example.
Patent application JP2010-209169 explains that this property can be
improved by adding a neopentyl polyol fatty acid ester, the fatty
acid being a C.sub.4-20 fatty acid, such as pentaerythritol fatty
tetra-acid esters, for example.
However, the current applicants surprisingly noticed that the use
of a pentaerythritol ester as a separation agent in alcohol-based
dry-erasable inks allowed inks to be obtained having good long-term
erasure properties, but only for certain surfaces (polypropylene,
PVC and enamel) and that conversely the erasure properties just
after the ink was applied, i.e. still wet ink, were
insignificant.
The applicants also discovered that in order to improve these
erasure performances both in the long-term on any board surface and
in the short term (at T0), i.e. still wet ink, it was necessary to
use pentaerythritol ester in association with glycerol and a
glycol, particularly triethylene glycol, because these three
compounds present a synergy if used together.
Application EP0551913 explains that pentaerythritol esters like
pentaerythritol tetraoctanoate must be used as a separation agent
in association with another separation agent to improve the erasure
properties. However, this other separation agent is a
polyoxyethylene-polyoxypropylene block copolymer.
Application JPH0428777 in turn explains that the pentaerythritol
fatty tetra-acid ester must be used as a separation agent in
association with two other separation agents to improve the erasure
properties. However, these two other separation agents are an
aliphatic monocarboxylic acid ester with at least 8 carbon atoms
and an aliphatic monohydric alcohol with at least 8 carbon atoms
and an alkylene polyoxyethylene phenyl ether phosphoric acid
ester.
DETAILED DESCRIPTION
The present disclosure also relates to an alcohol-based
dry-erasable ink for a writing instrument comprising, as separation
agent, a mixture of glycerol, triethylene glycol and
pentaerythritol ester.
In the sense of the present disclosure, "dry-erasable ink" is
understood as an ink that can be dry-erased on the support, even
after drying, simply by rubbing, without the use of water or
another solvent, e.g. using a dry cloth.
The dry-erasable ink according to the present disclosure thus
comprises, as separation agent, a mixture of glycerol, glycol and
pentaerythritol ester, advantageously a mixture of glycerol,
triethylene glycol and pentaerythritol ester.
The pentaerythritol ester may be a pentaerythritol fatty tetra-acid
ester, particularly C.sub.4-C.sub.20 fatty tetra-acid.
Advantageously it is an ester of the following general formula
(I)
##STR00001##
wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 represent,
independently of one another, a C.sub.4-C.sub.20 alkyl group, for
example a C.sub.6-C.sub.12 alkyl group or a C.sub.8-C.sub.10 alkyl
group.
In the sense of the present disclosure, "C.sub.4-C.sub.20 alkyl
group" is understood as any linear or ramified saturated alkyl
group comprising between 4 and 20 carbon atoms. These include, for
example, butyl, pentyl, hexyl, heptyl, ethylhexyl, octyl, decyl,
nonyl, undecyl and dodecyl.
As a pentaerythritol ester according to the disclosure we can
mention, for example, pentaerythrityl tetraethylhexanoate,
pentaerythrityl tetracaprylate/tetracaprate, pentaerythrityl
tetracaprylate, pentaerythrityl tetracaprate and their
mixtures.
Advantageously, it is pentaerythrityl tetraethylhexanoate.
These esters are commercially available from the company
STEARINERIE DUBOIS in particular.
The pentaerythritol ester content of the ink is between 0.1% and
25%, in some examples between 1% and 20%, or between 5% and 8%, and
in other examples between 5% and 7% by weight in relation to the
total weight of the ink.
In a particular embodiment the glycerol content of the ink is
between 0.1% and 10%, in some examples between 0.5% and 7%, or
between 1% and 5%, and in other examples between 2% and 4% by
weight in relation to the total weight of the ink.
The glycol that can be used as a separation agent in the
dry-erasable ink may be, for example, butylene glycol, propylene
glycol, hexylene glycol, a polyoxyalkylene glycol such as
triethylene glycol, dipropylene glycol or tripropylene glycol.
Advantageously, it is a polyoxyalkylene glycol such as triethylene
glycol, dipropylene glycol or tripropylene glycol.
Even more the glycol is triethylene glycol.
In a further embodiment the glycol content, particularly
triethylene glycol, of the ink according to the disclosure is
between 0.1% and 5%, in some examples between 0.3% and 4%, and in
other examples between 0.5% and 2% by weight in relation to the
total weight of the ink.
The ink according to the present disclosure is alcohol based. It
thus comprises as a principal solvent (i.e. as solvent present in
the largest quantity) an alcohol. The alcohol is an alcohol of the
general formula R.sub.4--OH in which R.sub.4 represents a
C.sub.1-C.sub.6 alkyl group, particularly a C.sub.1-C.sub.4 alkyl
group. The alcohol is chosen from among ethanol, propanol (e.g.
isopropanol and/or n-propanol), butanol (e.g. isobutanol,
n-butanol, sec-butanol and/or tert-butanol) and their mixtures, for
example, from among ethanol, propanol and their mixtures, and in
other examples from among n-propanol, ethanol and their
mixtures.
In particular, the alcohol content of the ink is between 40% and
90%, in some examples between 60% and 87%, in other examples
between 75 and 85% by weight in relation to the total weight of the
ink.
The alcohol-based ink may comprise a further solvent such as an
organic solvent that will particularly evaporate quickly and thus
having a low boiling point.
The alcohol-based ink according to the present disclosure does not
contain a further solvent.
The dry-erasable ink according to the disclosure furthermore
comprises a pigment, a resin and possibly additives.
The pigment allows color to be added to the ink and is chosen from
among pigments that are well known by a person skilled in the art.
These pigments include Pigment Blue 15:6 and Pigment Violet 37, for
example, which allow the color blue to be obtained.
The pigment content of the ink is between 0.1% and 10%, in some
examples between 0.5% and 5%, in other examples between 1% and 3%,
or between 1% and 2% by weight in relation to the total weight of
the ink.
The resin present in the ink allows the appropriate viscosity for
writing and adherence to the impermeable writing surface to be
added. The resin will furthermore create a film with the pigment
after evaporation of the alcohol.
The resin is alcohol-soluble. The resin may be a vinyl resin, an
acrylic resin, a styrene-acrylic resin, a maleic styrene-acid
copolymer resin, a maleic rosin-acid copolymer resin, a phenol
resin, a cellulosic resin, a ketone resin or a mixture of these.
The resin is a vinyl resin such as a vinyl chloride copolymer,
polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl acetate,
vinyl-pyrrolidone and vinyl-acetate copolymer or a mixture of
these. In particular, the resin is polyvinyl butyral.
In a particular embodiment, the resin content of the ink is between
0.1% and 10%, in some examples between 0.5% and 5%, in other
examples between 0.7% and 3%, or between 1% and 2% by weight in
relation to the total weight of the ink.
The dry-erasable ink may furthermore comprise additives such as
surfactants (e.g. anionic, cationic or non-ionic surfactants such
as laureth-3, phosphated alcohol ethoxylate or their mixtures),
manufacturing additives (e.g. esters such as triglycerides,
particularly C7, C8 and/or C10 triglycerides), denaturing agents
(e.g. esters such as diethylhexyl adipate), drying retarders (e.g.
esters or paraffins such as sorbitan stearate) and their
mixtures.
The additive content of the ink is between 0.1% and 10%, in some
examples between 0.5% and 5%, in other examples between 0.7% and
4%, or between 2% and 3% by weight in relation to the total weight
of the ink.
In a particular embodiment, the compound does not compromise
polyoxyethylene-polyoxypropylene block copolymer.
In fact, contrary to the indications in application EP0551913, the
presence of such a copolymer is not necessary in the ink to obtain
good erasure properties.
In a particular embodiment, the compound does not comprise alkylene
polyoxyethylene phenyl ether phosphoric acid ester or aliphatic
monocarboxylic acid ester with at least 8 carbon atoms and
aliphatic monohydric alcohol with at least 8 carbon atoms or a
mixture of these esters.
In fact, contrary to the indications in application JPH0428777, the
presence of these two esters is not necessary in the ink to obtain
good erasure properties.
The dry-erasable ink according to the disclosure is thus provided
for a writing instrument, such as a pen or marker, for example, a
marker, particularly a marker with a fibrous tip.
The marker may have a round-tip or beveled tip, for example.
The dry-erasable ink according to the disclosure is provided for
use on a non-porous surface, particularly a smooth surface, such as
a whiteboard, for example. This writing board may have a surface of
varying composition. It may be an enamel board, a glossy board, a
board covered with a polypropylene film, a board covered with a PVC
film or a board covered with melamine.
The present disclosure furthermore relates to a writing instrument
comprising a dry-erasable ink according to the invention.
The writing instrument is a pen or marker, particularly a marker,
more particularly one with a fibrous tip.
The marker may have a round-tip or beveled tip, for example.
The present disclosure will be understood after reading the example
the follows, provided as a non-limiting example.
Example 1
The short-term (wet or dry) and long-term erasure properties are
tested for different dry-erasable ink compounds: an ink compound
according to the disclosure comprising as separation agent a
mixture of glycerol, triethylene glycol and pentaerythritol ester
(example 1), a comparative ink compound comprising as separation
agent only a pentaerythritol ester (comp. example 1), a comparative
ink compound comprising as separation agent a mixture of
pentaerythritol ester and glycerol (comp. example 2), a comparative
ink compound comprising as separation agent a mixture of
pentaerythritol ester and triethylene glycol (comp. example 3) and
a comparative ink compound comprising as separation agent a mixture
of triethylene glycol and glycerol (comp. example 4). The
composition of these different blue inks is indicated in table 1
below.
TABLE-US-00001 TABLE 1 composition of inks in % by weight. Comp.
Comp. Comp. Comp. Ex 1 Ex 1 Ex 2 Ex 3 Ex 4 ETHANOL 69.84 73.80
69.84 69.84 69.84 PROPANOL-1 14.00 14.00 14.00 14.00 14.00 PIGMENT
BLUE 15:6 1.47 1.47 1.47 1.47 1.47 PIGMENT VIOLET 37 0.39 0.39 0.39
0.39 0.39 POLYVINYL 1.76 1.76 1.76 1.76 1.76 BUTYRAL TRIGLYCERIDE
C7 0.73 0.73 0.73 0.73 0.73 TRIGLYCERIDE 1.00 C8/C10
PENTAERYTHRITYL 6.00 6.00 6.00 6.00 TETRAETHYL- HEXANOATE GLYCEROL
3.00 4.00 3.00 TRITHYLENE 1.00 4.00 1.00 GLYCOL DIETHYLHEXYL 0.71
0.75 0.71 0.71 0.71 ADIPATE DIISODECYL 5.00 ADIPATE SORBITAN
STEARATE 0.80 0.80 0.80 0.80 0.80 LAURETH-3 0.15 0.15 0.15 0.15
0.15 PHOSPHATED 0.15 0.15 0.15 0.15 0.15 ALCOHOL ETHOXYLATE TOTAL
100.0 100.0 100.0 100.0 100.0
The details of the tests performed to compare the erasability at T0
and over time between the inks are as follows: Erasability at
T0:
This test evaluates the erasability of an ink deposit when it is
still wet and when it is dry, as well as the erasability incidence
on the support.
The test is performed in a room with air conditioning and
controlled humidity: 23.degree. C. (+/-2.degree. C.)/50% relative
humidity (+/-5%)
The test is performed on two different surfaces: Velleda.RTM. slate
(polypropylene film) and a whiteboard with a melamine surface.
Before beginning the tests, the investigator must clean the
different supports with ethanol, leave them to dry for 5 minutes,
wash his hands and dry them.
Three tests are performed: Erasability of the wet mark (before
cloth): this test allows the investigator to verify that the
erasure is clean when the consumer makes a mistake, for example,
and wants to erase his marking immediately without waiting the
drying time of the film on the support.
The procedure involves making, on each of the surfaces to be
tested, a smear with the dimensions 20.times.80 mm and immediately
wiping the smear with 2 fingers in a circular movement until the
smear has completely disappeared.
This step is repeated 5 times in a row as quickly as possible and
by making the smear in exactly the same spot (without cleaning the
support between wipings) and a score is given based on what remains
visible on the support according to a scale indicated in table 2
below, ranging from 0 to 10.
TABLE-US-00002 TABLE 2 score based on observation Observation No
Light Moderate Large Very large mark mark mark mark mark Score 10
7.5 5 2.5 0
Erasability of the wet mark (after cloth):
If a mark remains, the support is cleaned with absorbent paper (3
times at most) and a score is also given based on what remains
visible on the support with the same scale above, ranging from 0 to
10, from table 2. Erasability of the dry mark: habitual consumer
use
The procedure involves making, on each of the surfaces to be
tested, a smear with the dimensions 20.times.80 mm and letting it
dry for 5 minutes. The smear is then cleaned with an absorbent
paper in a back-and-forth motion until the smear has completely
disappeared.
This is repeated 3 times in a row making the smear in exactly the
same spot (without cleaning the support between wipings) and a
score is given based on what remains visible on the support with
the same scale above, ranging from 0 to 10, from table 2.
Erasability Over Time:
This test evaluates how long a dry-erasable ink deposit adheres to
a given surface before it can no longer be erased. The test is
performed in a room with air conditioning and controlled humidity:
23.degree. C. (+/-2.degree. C.)/50% relative humidity (+/-5%).
The test is performed on different surfaces: Velleda.RTM. slate
(polypropylene film) a PCVC film a whiteboard with a melamine
surface purchased on the European market a whiteboard with a
melamine surface from the USA a whiteboard with a glossy surface
(purchased on the European market) a whiteboard with an enamel
surface (purchased on the European market)
Before beginning the tests, the investigator must clean the
different supports with ethanol and leave them to dry for 5
minutes.
The procedure involves vertically making as many smears (with the
dimension 10.times.10 mm) as aging intervals as desired on each of
the surfaces to be tested. After each aging interval and for each
support, the smear is cleaned with a clean absorbent paper in a
quick, fluid back-and-forth motion without pressing too hard.
The test is stopped once the ink adheres to the support or can no
longer be erased at all.
In standard procedure this test is performed until 3 months, but
for the ink according to the disclosure (ex 1), the test is
extended beyond 3 months.
The erasure result, expressed in time, corresponds to the aging
interval preceding the adherence of the ink or the non-erasure of
the ink. The results obtained with the different inks are presented
in table 3 below.
TABLE-US-00003 TABLE 3 Results of the erasure tests Tests Surface
Ex 1 Comp Ex 1 Comp Ex 2 Comp Ex 3 Comp Ex 4 Erasability Wet
Velleda .RTM. 7.5 2.5 5 5 7.5 at T0 mark Melamine 5 0 2.5 2.5 5
(score) before cloth Wet Velleda .RTM. 10 10 10 10 10 mark Melamine
10 10 10 10 10 after cloth Dry Velleda .RTM. 10 10 10 10 10 mark
Melamine 10 10 10 10 10 Erasability over Velleda .RTM. Between 3
months 3 months 3 months Between time (in time) 7 and 8 OK OK OK 1
and 2 months weeks PVC film >12 3 months 3 months 3 months
Between months OK OK OK 2 and 3 months Melamine >12 3 months
<1 day <1 day 3 months (EU) months OK OK Melamine >12
Between <1 day <1 day Between (USA) months 1 and 2 1 and 2
months months Gloss Between Between Between Between Between 3 and 4
1 and 3 1 and 3 1 and 3 1 and 3 months days days days days Enamel
>12 3 months Between 3 months 3 months months OK 1 and 2 OK OK
weeks
Only the ink according to the disclosure (Ex 1) allows good
erasability properties to be obtained at T0, particularly when the
ink is still wet, and over time, regardless of the surface on which
the mark is made.
The use of the 3 separation agents, pentaerythritol ester, glycerol
and triethylene glycol therefore has synergic properties on the
erasure properties.
* * * * *